CN107349947A - A kind of acetic acid hydrogenation catalyst and its application - Google Patents

A kind of acetic acid hydrogenation catalyst and its application Download PDF

Info

Publication number
CN107349947A
CN107349947A CN201710373077.7A CN201710373077A CN107349947A CN 107349947 A CN107349947 A CN 107349947A CN 201710373077 A CN201710373077 A CN 201710373077A CN 107349947 A CN107349947 A CN 107349947A
Authority
CN
China
Prior art keywords
acetic acid
hydrogenation catalyst
acid hydrogenation
carbonate
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710373077.7A
Other languages
Chinese (zh)
Other versions
CN107349947B (en
Inventor
蒲延芳
黄龙
赵素云
李景斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHEYANG SANJU KAITE CATALYST Co Ltd
Beijing Institute of Petrochemical Technology
Original Assignee
SHEYANG SANJU KAITE CATALYST Co Ltd
Beijing Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SHEYANG SANJU KAITE CATALYST Co Ltd, Beijing Institute of Petrochemical Technology filed Critical SHEYANG SANJU KAITE CATALYST Co Ltd
Priority to CN201710373077.7A priority Critical patent/CN107349947B/en
Publication of CN107349947A publication Critical patent/CN107349947A/en
Application granted granted Critical
Publication of CN107349947B publication Critical patent/CN107349947B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

A kind of acetic acid hydrogenation catalyst provided by the invention, including active component and carrier, it is preferred that emphasis is also include the carbonate of one or both of calcium and barium.The generation of strong alkaline substance is avoided while reducing catalyst acid amount using calcium carbonate and barium carbonate in the present invention, and then catalyst surface solid alkali number is declined to a great extent, it is achieved thereby that acetic acid hydrogenation catalyst its alkali number while catalyst acid amount is reduced also does not improve, and then avoid the generation of accessory substance acetone, isopropanol.

Description

A kind of acetic acid hydrogenation catalyst and its application
Technical field
The present invention relates to catalyst field, and in particular to a kind of acetic acid hydrogenation catalyst and its application.
Background technology
Ethanol is a kind of important chemical industry, medicine, the energy and raw-food material.Acetic acid preparation of ethanol through hydrogenation is industrial at present Prepare one of common method of ethanol.This method, which prepares ethanol, mainly includes two kinds of approach, first, acetic acid generates acetic acid through esterification Ester, then acetate is hydrogenated to ethanol, then carries out refined raw producing and ethanol product；Second, acetic acid direct hydrogenation generates ethanol, then Alcohol product is produced through subtractive process.No matter it is above-mentioned which kind of prepare ethanol during, can all produce substantial amounts of accessory substance such as first Alkane, ethane, carbon monoxide, acetaldehyde, ether, ethyl acetate and acetone etc..And the catalyst used in hydrogenation process, can be effective Reduction accessory substance generation, improve the yield of ethanol.Influenceing the catalytic performance of acetic acid hydrogenation catalyst mainly has two aspects, First, the acidic site of catalyst surface, the bronsted acid position of catalyst surface can promote ethanol to be converted into ethyl acetate, drop The yield of low ethanol, second, active component, it influences the catalytic activity of catalyst, the catalysis currently used for acetic acid preparation of ethanol by hydrogenating The active component of agent is mostly noble metal, such as Pt, Ag, in the preparation of scale ethanol, frequently can lead to planning and cost It is too high, and the surface acidity position of catalyst is not modified, so that existing acetic acid hydrogenation catalyst is in catalytic process Poor selectivity.
In the prior art, a kind of methods with acetate preparation of ethanol through hydrogenation of Chinese patent literature CN102093162B, The active component for disclosing the catalytic hydrogenation catalyst used is copper, and carrier is silica, and with transition metal or/and alkali gold One or more in category are as auxiliary agent；And define source for silicate etc., and also define alkali metal for magnesium and One kind in barium.Abandoned in above-mentioned catalyst and used noble metal to reduce the cost of catalyst, and make as active component With the carrier of silicate, the acidic site of catalyst surface is decreased, but above-mentioned patent is reducing support surface acidity position The alkalescence of carrier surface is improved simultaneously, but the increase of catalyst surface alkalescence can cause the amount of accessory substance acetone to increase Add, and then reduce the yield of ethanol, while during caused by acetone, can also by-product carbon dioxide, cause recycle hydrogen Inert gas in gas accumulates, and so as to need to discharge a part from circulating air, i.e., so-called periodic off-gases, this can cause to add Hydrogen gas consumption increase during hydrogen, and acetone can be converted into isopropanol in hydrogen, but isopropanol and ethanol are due to boiling Point is close, is very difficult to separation, can not often separate, and this has resulted in containing substantial amounts of isopropanol impurity in ethanol, This point has related narration in patent CN102414150A, in turn results in the adverse effect to alcohol product property.
Acetone and isopropanol are the problem in acetic acid preparation of ethanol by hydrogenating, such as SalvadorAnd Enrique (article is published in the catalysis meeting of North America in 2009 for the acetic acid gas phase hydrogenation reaction that Iglesia has investigated on the ruthenium-based catalyst of load View), reaction condition is：150~350 DEG C of temperature, normal pressure；Acetone is one of main accessory substance, in extreme situations acetone Selectivity can reach 40%.Author has also investigated acetic acid conversion situation during using pure carrier as catalyst, finds pure Also there is the production of acetone on carrier, can reach 30% or so in the case of extreme；Author thinks that the generation of acetone is also due to The surface alkalinty of catalyst causes.Therefore while catalyst surface acidity is reduced, it is also most important to reduce surface alkalinty , but for now, people's concern is very few.
The content of the invention
Therefore, the technical problem to be solved in the present invention is to overcome is reducing the same of support surface acidity position in the prior art When add carrier surface alkalescence, so as to cause accessory substance acetone, isopropanol amount increase, reduce ethanol yield and purity lack Fall into, so as to provide a kind of acetic acid hydrogenation catalyst and its application.
A kind of acetic acid hydrogenation catalyst, including active component and carrier, in addition to regulation component, the regulation component is alkali One or more in metal and/or alkaline earth metal carbonate.
Preferably, in described acetic acid hydrogenation catalyst, it is described regulation component be selected from calcium carbonate, potassium carbonate, magnesium carbonate, One or more in sodium carbonate and barium carbonate.
Preferably, in described acetic acid hydrogenation catalyst, the regulation component is calcium carbonate and/or barium carbonate.
Preferably, in described acetic acid hydrogenation catalyst, the crystalline phase granularity of the carbonate is 2-20nm.
Preferably, in described acetic acid hydrogenation catalyst, the regulation component accounts for the total matter of acetic acid hydrogenation catalyst The 0.5-8wt% of amount.
Preferably, in described acetic acid hydrogenation catalyst, described hydrogenation catalyst composition formula is ABC@S；
A and B is the active component, and C is the regulation component, and S is the carrier；
Wherein, the active component A is selected from the oxide of cobalt and/or copper；The active component B is selected from tin, tungsten, molybdenum and iron Oxide in one or more；
The carrier S is selected from silica, zirconium oxide or activated carbon.
Preferably, in described acetic acid hydrogenation catalyst, the active component A, the active component B and the regulation Component C mol ratio is：1：(0.5-1.1)：(0.05-0.2).
Preferably, in described acetic acid hydrogenation catalyst, in terms of the gross mass of the acetic acid hydrogenation catalyst,
The content of the active component A is 15-30%；
The content of the active component B is 10-40%；
The content of the carrier S is 10-55%.
A kind of acetic acid hydrogenation catalyst of the present invention, the application in acetic acid preparation of ethanol through hydrogenation is catalyzed.
Technical solution of the present invention, have the following advantages that：
1. a kind of acetic acid hydrogenation catalyst provided by the invention, including active component and carrier, it is preferred that emphasis is also including calcium, One or more of carbonate in potassium, magnesium, sodium and barium.Alkali carbonate and/or alkaline-earth metal carbonic acid are used in the present invention Salt regulation reduces the acid amount of catalyst, while using the electron-withdrawing property being greatly reduced of carbonate, reduces the alkali of strong basicity Metal and/or the amount of alkaline earth oxide generation, carry out so that base strength declines to a great extent, it is achieved thereby that acetic acid hydrogenation is urged The agent effect that its alkali number does not also improve while catalyst acid amount is reduced, and then avoid due to catalyst alkali number mistake Height, cause have the problem of accessory substance acetone, isopropanol generation.
2. a kind of acetic acid hydrogenation catalyst provided by the invention, selects the carbonate of suitable crystalline phase size, avoids After carbonate crystalline phase size is more than 20nm, its load factor is influenceed, and then influences the ability to the acid regulation of catalyst surface.
Embodiment
Technical scheme will be clearly and completely described below, it is clear that described embodiment is this hair Bright part of the embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art exist The every other embodiment obtained under the premise of creative work is not made, belongs to the scope of protection of the invention.Under in addition, As long as involved technical characteristic does not form conflict can phase each other in the different embodiments of the present invention described by face Mutually combine.
Embodiment 1
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps：
(1) cobalt nitrate and calcium nitrate are added to the water, after stirring, add ferric nitrate and nitric acid tin, after stirring, Obtain soak；
(2) sodium carbonate is added into the soak, forms precipitated liquid, silica is added into the precipitated liquid and is carried Body, 3h is cured in the case where temperature is 80 DEG C of hydrothermal condition, was filtrated to get filter solid；
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, is 100 DEG C in temperature After lower drying, in 300 DEG C of roastings, the catalyst precursor is obtained；
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure For 150kpa, control the temperature in reaction vessel to be in 50 DEG C, carbonization treatment 20h, that is, obtain the acetic acid that formula is ABC S and be hydrogenated with Catalyst.
Wherein, in the acetic acid hydrogenation catalyst prepared in the present embodiment, the oxidation of the oxide of cobalt, the oxide of tin, iron Thing, calcium carbonate and carrier silicas account for 15%, 20%, 10%, 3% and the 52% of acetic acid hydrogenation catalyst gross mass respectively.
Embodiment 2
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps：
(1) copper nitrate and calcium nitrate are added to the water, after stirring, add ferric nitrate and nitric acid molybdenum, after stirring, Obtain soak；
(2) sodium carbonate is added into the soak, forms precipitated liquid, silica is added into the precipitated liquid and is carried Body, 5h is cured in the case where temperature is 70 DEG C of hydrothermal condition, was filtrated to get filter solid；
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, in the case where temperature is 80 DEG C After drying, in 600 DEG C of roastings, the catalyst precursor is obtained；
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure For 250kpa, control the temperature in reaction vessel to be in 70 DEG C, carbonization treatment 30h, that is, obtain the acetic acid that formula is ABC S and be hydrogenated with Catalyst.
Wherein, in the acetic acid hydrogenation catalyst prepared in the present embodiment, the oxidation of the oxide of copper, the oxide of molybdenum, iron Thing, calcium carbonate and carrier silicas account for 35%, 2%, 12% and the 4% and 47% of acetic acid hydrogenation catalyst gross mass respectively.
Embodiment 3
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps：
(1) copper nitrate and barium nitrate are added to the water, after stirring, add nitric acid tungsten and nitric acid molybdenum, after stirring, Obtain soak；
(2) sodium carbonate is added into the soak, precipitated liquid is formed, Zirconia carrier is added into the precipitated liquid, 1h is cured in the case where temperature is 90 DEG C of hydrothermal condition, was filtrated to get filter solid；
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, is 150 DEG C in temperature After lower drying, in 450 DEG C of roastings, the catalyst precursor is obtained；
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure For 200kpa, control the temperature in reaction vessel to be in 20 DEG C, carbonization treatment 12h, that is, obtain the acetic acid that formula is ABC S and be hydrogenated with Catalyst.
Wherein, in the acetic acid hydrogenation catalyst prepared in the present embodiment, the oxidation of the oxide of copper, the oxide of molybdenum, tungsten Thing, barium carbonate and carrier Zirconia carrier account for 20%, 10%, 30%, 0.5% and of acetic acid hydrogenation catalyst gross mass respectively 39.5%.
Embodiment 4
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps：
(1) cobalt nitrate and magnesium nitrate are added to the water, and after stirring, add nitric acid tin and ferric nitrate, after stirring, obtain To soak；
(2) sodium carbonate is added into the soak, precipitated liquid is formed, absorbent charcoal carrier is added into the precipitated liquid, 5h is cured in the case where temperature is 80 DEG C of hydrothermal condition, was filtrated to get filter solid；
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, is 150 DEG C in temperature After lower drying, in 500 DEG C of roastings, the catalyst precursor is obtained；
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure For 170kpa, control the temperature in reaction vessel to be in 100 DEG C, carbonization treatment 48h, that is, obtain the acetic acid that formula is ABC S and add Hydrogen catalyst.
Wherein, in the acetic acid hydrogenation catalyst prepared in the present embodiment, the oxidation of the oxide of cobalt, the oxide of tin, iron Thing, magnesium carbonate and carrier active carbon account for 30%, 5%, 5% and the 8% and 52% of acetic acid hydrogenation catalyst gross mass respectively.
Embodiment 5
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps：
(1) cobalt nitrate and sodium nitrate are added to the water, after stirring, add ferric nitrate and nitric acid tin, after stirring, Obtain soak；
(2) sodium carbonate is added into the soak, forms precipitated liquid, silica is added into the precipitated liquid and is carried Body, 3h is cured in the case where temperature is 80 DEG C of hydrothermal condition, was filtrated to get filter solid；
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, is 100 DEG C in temperature After lower drying, in 500 DEG C of roastings, the catalyst precursor is obtained；
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure For 220kpa, control the temperature in reaction vessel to be in 80 DEG C, carbonization treatment 30h, that is, obtain the acetic acid that formula is ABC S and be hydrogenated with Catalyst.
Wherein, in the acetic acid hydrogenation catalyst prepared in the present embodiment, the oxidation of the oxide of cobalt, the oxide of tin, iron Thing, sodium carbonate and carrier silicas account for 15%, 20%, 10% and the 3% and 52% of acetic acid hydrogenation catalyst gross mass respectively.
Comparative example 1
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps：
(1) copper nitrate and calcium nitrate are added to the water, after stirring, add ferric nitrate and nitric acid molybdenum, after stirring, Obtain soak；
(2) sodium carbonate is added into the soak, forms precipitated liquid, silica is added into the precipitated liquid and is carried Body, 5h is cured in the case where temperature is 70 DEG C of hydrothermal condition, was filtrated to get filter solid；
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, in the case where temperature is 80 DEG C After drying, in 600 DEG C of roastings, acetic acid hydrogenation catalyst is obtained；
Wherein, in the acetic acid hydrogenation catalyst prepared in the present embodiment, the oxidation of the oxide of copper, the oxide of molybdenum, iron Thing, the oxide of calcium and carrier silicas account for 35%, 2%, 12% and 4% and of acetic acid hydrogenation catalyst gross mass respectively 47%.
Comparative example 2
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps：
10wt% cobalts and 1wt% chromium are prepared on graphite.
The uniform particle size with about 0.2mm through being milled and sieving is distributed at 120 DEG C in a nitrogen atmosphere in an oven Graphite dry the whole night, is cooled to room temperature.Chromic nitrate nonahydrate, the solution in distilled water are added thereto.Will be resulting Slurries are dried in 110 DEG C of baking oven is progressively heated at.Then the catalyst mixture through dipping is calcined at 500 DEG C (6h, 1 ℃/min).Solution of the Cobalt(II) nitrate hexahydrate in distilled water is added into the material through calcining and cooling down.Will be resulting Slurries are progressively heated in 110 DEG C of baking oven and dried, then calcine the catalyst mixture through dipping at 500 DEG C (6h, 1 DEG C/ min)。
Compliance test result
1. the effect of acetic acid hydrogenation catalyst prepared by couple embodiment 1-5 and comparative example 1-2 detects, testing result It is shown in Table 1.
Testing conditions：220-230 DEG C, hydracid compares 30-50；Liquid hourly space velocity (LHSV) 0.4-0.8；
Table 1
2. acetic acid hydrogenation catalyst surface alkali number and acid amount prepared by couple embodiment 1-5 and comparative example 1-2 detect, Testing result is shown in Table 2.
Surface acidity assay method：
Surface acidity uses temperature programmed desorption ammonia (NH3- TPD) method, in Micromeritics Auto Carried out on Chem.2920 (USA), catalyst sample (150mg) is pre-processed into 3h for 350 DEG C in Ar streams first, is then cooled to 50 DEG C, it is passed through NH3Adsorb 30min, in Ar purging to baseline it is steady after start to warm up to 600 DEG C desorption ammonia (heating rates 10 DEG C/min), one is done to each catalyst and does not adsorb NH3Blank roasting experiment.Containing for 0.5ml is entered using pulse 5vol% NH3-Ar gaseous mixtures are demarcated to thermal conductivity cell detector (TCD) to be measured with gauging surface acid.
Surface alkali number measure method：
Surface alkali number uses temperature programmed desorption ammonia (CO2- TPD) method, in Micromeritics Auto Carried out on Chem.2920 (USA), catalyst sample (150mg) is pre-processed into 3h for 350 DEG C in He streams first, is then cooled to 50 DEG C, it is passed through CO2Adsorb 30min, in He purging to baseline it is steady after start to warm up to 600 DEG C desorption CO2(heating rate 10 DEG C/min), a not CO absorption is done to each catalyst2Blank roasting experiment.Containing for 0.5ml is entered using pulse 5vol% CO2-He gaseous mixtures are demarcated with gauging surface alkali number to thermal conductivity cell detector (TCD).
Table 2
3. the crystal grain chi of the regulation component loaded on the acetic acid hydrogenation catalyst prepared with x-ray diffractometer embodiment 1-3 Little progress row detects, and is calculated according to ScheHer formula, and testing result is shown in Table 3.
Table 3
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or Among changing still in the protection domain of the invention.

Claims (9)

1. a kind of acetic acid hydrogenation catalyst, including active component and carrier, it is characterised in that also include regulation component, the tune It is the one or more in alkali metal and/or alkaline earth metal carbonate to save component.
2. acetic acid hydrogenation catalyst according to claim 1, it is characterised in that the regulation component is selected from calcium carbonate, carbon One or more in sour potassium, magnesium carbonate, sodium carbonate and barium carbonate.
3. acetic acid hydrogenation catalyst according to claim 1 or 2, it is characterised in that it is described regulation component be calcium carbonate and/ Or barium carbonate.
4. according to any described acetic acid hydrogenation catalysts of claim 1-3, it is characterised in that the crystallite dimension of the carbonate For 2-20nm.
5. according to any described acetic acid hydrogenation catalysts of claim 1-4, it is characterised in that the regulation component accounts for the vinegar The 0.5-8wt% of sour hydrogenation catalyst gross mass.
6. according to any described acetic acid hydrogenation catalysts of claim 1-5, it is characterised in that described hydrogenation catalyst composition Formula is ABC@S；
A and B is the active component, and C is the regulation component, and S is the carrier；
Wherein, the active component A is selected from the oxide of cobalt and/or copper；The active component B is selected from the oxygen of tin, tungsten, molybdenum and iron One or more in compound；
The carrier S is selected from silica, zirconium oxide or activated carbon.
7. according to any described acetic acid hydrogenation catalysts of claim 1-6, it is characterised in that the active component A, the work Property the component B and regulation component C mol ratio be：1：(0.5-1.1)：(0.05-0.2).
8. the acetic acid hydrogenation catalyst according to claim 6 or 7, it is characterised in that with the acetic acid hydrogenation catalyst Gross mass meter,
The content of the active component A is 15-30%；
The content of the active component B is 10-40%；
The content of the carrier S is 10-55%.
9. the acetic acid hydrogenation catalyst described in a kind of any one of claim 1-8, answering in acetic acid preparation of ethanol through hydrogenation is catalyzed With.
CN201710373077.7A 2017-05-24 2017-05-24 Acetic acid hydrogenation catalyst and application thereof Active CN107349947B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710373077.7A CN107349947B (en) 2017-05-24 2017-05-24 Acetic acid hydrogenation catalyst and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710373077.7A CN107349947B (en) 2017-05-24 2017-05-24 Acetic acid hydrogenation catalyst and application thereof

Publications (2)

Publication Number Publication Date
CN107349947A true CN107349947A (en) 2017-11-17
CN107349947B CN107349947B (en) 2020-05-19

Family

ID=60271757

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710373077.7A Active CN107349947B (en) 2017-05-24 2017-05-24 Acetic acid hydrogenation catalyst and application thereof

Country Status (1)

Country Link
CN (1) CN107349947B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108358752A (en) * 2018-04-18 2018-08-03 肖锦 A kind of method of acetic acid hydrogenation ethyl alcohol

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103787830A (en) * 2012-10-31 2014-05-14 中国石油化工股份有限公司 Method for producing ethanol by acetic acid hydrogenation
CN103785413A (en) * 2012-10-31 2014-05-14 中国石油化工股份有限公司 Hydrogenation catalyst, and preparation method and application thereof
CN103785414A (en) * 2012-10-31 2014-05-14 中国石油化工股份有限公司 Carboxylic acid hydrogenation catalyst, preparation method and application thereof
CN104024192A (en) * 2011-11-22 2014-09-03 国际人造丝公司 Hydrogenating acetic acid to produce ethyl acetate and reducing ethyl acetate to ethanol
CN104211569A (en) * 2013-06-05 2014-12-17 中国石油化工股份有限公司 Method for production of ethanol by direct hydrogenation of acetic acid
CN105418372A (en) * 2014-09-18 2016-03-23 中国石油化工股份有限公司 Method for producing ethanol by acetic acid through hydrogenation
CN105481649A (en) * 2014-09-18 2016-04-13 中国石油化工股份有限公司 Method for preparing ethanol through hydrogenating acetic acid

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104024192A (en) * 2011-11-22 2014-09-03 国际人造丝公司 Hydrogenating acetic acid to produce ethyl acetate and reducing ethyl acetate to ethanol
CN103787830A (en) * 2012-10-31 2014-05-14 中国石油化工股份有限公司 Method for producing ethanol by acetic acid hydrogenation
CN103785413A (en) * 2012-10-31 2014-05-14 中国石油化工股份有限公司 Hydrogenation catalyst, and preparation method and application thereof
CN103785414A (en) * 2012-10-31 2014-05-14 中国石油化工股份有限公司 Carboxylic acid hydrogenation catalyst, preparation method and application thereof
CN104211569A (en) * 2013-06-05 2014-12-17 中国石油化工股份有限公司 Method for production of ethanol by direct hydrogenation of acetic acid
CN105418372A (en) * 2014-09-18 2016-03-23 中国石油化工股份有限公司 Method for producing ethanol by acetic acid through hydrogenation
CN105481649A (en) * 2014-09-18 2016-04-13 中国石油化工股份有限公司 Method for preparing ethanol through hydrogenating acetic acid

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108358752A (en) * 2018-04-18 2018-08-03 肖锦 A kind of method of acetic acid hydrogenation ethyl alcohol

Also Published As

Publication number Publication date
CN107349947B (en) 2020-05-19

Similar Documents

Publication Publication Date Title
CN103191720B (en) A kind of catalyst for methanation in presence of sulfur of magnesium aluminate spinel load
CN102151568A (en) Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof
CN103769148A (en) Acrolein oxidation to acrylic acid catalyst, preparation method and application of catalyst
CN111215084A (en) Copper-based catalyst for preparing methanol by carbon dioxide hydrogenation, preparation and application thereof
CN103769149A (en) Catalyst for preparing propenoic acid through oxidation of propenal, as well as preparation and application of catalyst
KR20130074843A (en) Catalyst for reforming of methane with the enhanced stability for sulfur components, preparing method thereof and methane reforming method using the catalyst
CN103357441B (en) Silver catalyst carrier, its preparation method, the catalyst be made up of it and application
ZHAO et al. Hydrogen production from steam reforming of ethylene glycol over supported nickel catalysts
EP2915582B1 (en) Composite oxide, preparation method for same, and application thereof
JP4890194B2 (en) Method for producing carbon monoxide removal catalyst
CN107349947A (en) A kind of acetic acid hydrogenation catalyst and its application
CN113441124A (en) Carbonyl sulfide hydrolysis catalyst and preparation method thereof
CN107321357A (en) A kind of preparation method and applications of acetic acid hydrogenation catalyst
CN115155582B (en) Activated carbon-loaded catalyst for preparing hydrogen by reforming methanol and preparation method and application thereof
JP5999569B2 (en) C2 oxygenate synthesis catalyst, C2 oxygenate production apparatus, and C2 oxygenate production method
CN106824177B (en) Catalyst for synthesizing oxalate by CO gas phase, preparation method and application
CN114433045B (en) Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method
CN111992209A (en) Catalyst for synthesizing dimethyl oxalate and preparation method and application thereof
KR101594901B1 (en) Cokes oven gas reforming catalyst for manufacturing synthesis gas, method for preparing the same and method for manufacturing synthesis gas from cokes oven gas using the same
KR20140002618A (en) Highly active water gas shift catalyst, preparation process and use thereof
CN112264026A (en) Preparation method of high-activity high-selectivity methanol synthesis catalyst
Daorattanachai et al. Catalytic Non-oxidative Dehydrogenation of Ethanol into Acetaldehyde and Hydrogen using Monometallic Cu, Ag and Bimetallic Cu-Ag Catalysts Supported by SiO2
CN106607024B (en) Catalyst for synthesizing oxalate by CO gas phase, preparation method and application
KR101220759B1 (en) Nickel catalyst supported on xerogel alumina and method for amnufacturing the same, and method for manufacturing methane using said catalyst
KR101525943B1 (en) Heterogeneous Cupper based catalysts for coproducing dimethyl ether and acetic acid from methanol

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant